TW202031811A - Active energy ray-curable ink, method for producing ink cured product, and printed matter - Google Patents

Abstract

Provided is an active energy ray-curable ink containing: a monomer having an ethylenically unsaturated double bond; and a photopolymerization initiator represented by general formula (1). Also provided are: a method for producing an ink cured product, the method involving performing printing by means of the active energy ray-curable ink, and curing the printed ink by means of an active energy ray; and a printed matter. (In general formula (1), R1 represents a linear or branched alkyl group having 1-10 carbon atoms or a vinyl group, Y represents a hydrogen atom, a linear or branched alkyl group having 1-10 carbon atoms, an aryl group having 6-10 carbon atoms, a linear or branched alkoxy group having 1-10 carbon atoms, or an aryloxy group having 6-10 carbon atoms.).

Description

Active energy ray curable printing ink, manufacturing method of printing ink hardened material and printed matter

The present invention relates to an active energy ray hardening ink, a method for manufacturing the hardened product of the active energy ray hardening ink, and printed matter.

Active energy ray-curable ink is solvent-free and the active energy ray hardens and dries instantaneously. Therefore, it can obtain environmentally compatible, excellent printing workability, and high-quality printed matter. It is used for lithographic printing (flat plate with dampened water). Printing or non-horizontal plate printing without dampening water), relief printing, gravure printing, stencil printing, or transfer of the ink attached to these plates to an intermediate transfer body such as a blanket, and then printing on the printed body The use of printing ink in various printing methods combined by the transfer (offset) method can be applied to various packaging printed materials such as foam printed materials, various book printed materials, carton paper, etc., various plastic printed materials, stickers, and label printed materials , Fine art prints, metal prints (art prints, beverage can prints, food prints such as cans), etc.

As the light source of these active energy ray-curable inks, low- or high-pressure mercury lamps, xenon lamps, metal halide lamps and other ultraviolet lamps (UV lamps) have been widely used in the past. In recent years, ultraviolet light-emitting diodes ( UV-LED) is used as the illumination module of the light source and is developing in the application of UV printing.

Ultraviolet light-emitting diodes (UV-LEDs) generate ultraviolet light with a peak wavelength of 350 to 420 nm. In other words, when it is desired to apply ink using conventional light sources such as metal halide lamps or high-pressure mercury lamps to UV-LEDs, it is necessary to use a photopolymerization initiator that absorbs around 350 to 420 nm. However, due to the ink The used pigment itself absorbs light in the wavelength range of 350 to 420 nm. Therefore, in most cases, even if a photopolymerization initiator having absorption at a wavelength of 350 to 420 nm is used, insufficient curing may occur.

啉基烷基苯酮化合物與二烷基胺基二苯酮化合物(A2-1)及/或噻噸酮化合物的活性能量線硬化型印墨(例如參照專利文獻1)；或併用作為光聚合起始劑的α-胺基烷基苯酮化合物與醯基膦氧化物化合物，且含有特定醇的活性能量線硬化型印墨(例如參照專利文獻2)。然而α-胺基烷基苯酮化合物係紫外線吸收區域位於較短波長側，在藉由UV-LED使其硬化的情況，會有塗膜表面的硬化性不佳的情形。又，作為α-

啉基烷基苯酮化合物所通用的2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙-1-酮(Irgacure907)，紫外線照射後會立即產生特殊的臭氣，因此在要求高衛生性的用途上，摻合量會有界限，而無法得到充分的硬化性。 [先前技術文獻] [專利文獻]As the ink composition suitable for UV-LED, for example, α-(dimethyl)aminoalkylphenone compound and/or α-

Active energy ray-curable ink (for example, refer to Patent Document 1) of a hydroxyalkyl phenone compound and a dialkylamino benzophenone compound (A2-1) and/or a thioxanthone compound; or used together as photopolymerization An active energy ray-curable ink containing an α-aminoalkylphenone compound and an phosphine oxide compound as a starter and a specific alcohol (for example, refer to Patent Document 2). However, the ultraviolet absorption region of the α-aminoalkylphenone compound is located on the shorter wavelength side, and when it is cured by UV-LED, the surface of the coating may have poor curing properties. Also, as α-

Common 2-methyl-1-[4-(methylthio)phenyl]-2-

Irgacure-1-one (Irgacure907) produces a special odor immediately after ultraviolet radiation. Therefore, in applications requiring high hygiene, there is a limit to the blending amount, and sufficient curability cannot be obtained. [Prior Art Document] [Patent Document]

[Patent Document 1] JP 2015-193677 A [Patent Document 2] JP 2011-236277 A

[The problem to be solved by the invention]

The inventors of the present invention provide an active energy ray-curable ink, which cures very quickly even when a UV-LED light source is used, and does not easily generate odor. [Means to solve the problem]

The inventors of the present invention have discovered that an active energy ray-curable ink containing a specific photopolymerization initiator can solve the above-mentioned problems.

That is, the present invention provides an active energy ray curable printing ink, which contains a monomer having an ethylenically unsaturated double bond and a photopolymerization initiator represented by the general formula (1).

(1)

(1)

(In the general formula (1), R ¹ represents a linear or branched alkyl group with 1 to 10 carbon atoms, or a vinyl group, Y represents a hydrogen atom, a linear or branched alkyl group with 1 to 10 carbon atoms, An aryl group with 6 to 10 carbon atoms, a linear or branched alkoxy group with 1 to 10 carbon atoms, or an aryloxy group with 6 to 10 carbon atoms)

In addition, the present invention provides a method for producing a cured ink for printing using the active energy ray hardening type ink described above, and curing the printed ink using the active energy ray.

In addition, the present invention provides a method for producing a cured ink using the active energy ray-curable ink described above for offset printing, and using the active energy ray to harden the printed ink.

In addition, the present invention provides a printed matter obtained by the above-described method of manufacturing an ink cured product. [Effects of Invention]

According to the present invention, an active energy ray curable ink can be obtained, which cures very quickly even when a UV-LED light source is used as an ultraviolet light source, and is less likely to generate odors. Therefore, it is also used in the field of packaging printing where hygiene is required. Can be used without problems. The printing ink of the present invention can be suitably used as printing inks in various printing methods, especially offset printing inks using dampening water.

[The form of implementing the invention]

(Photopolymerization initiator represented by the general formula (1)) In the photopolymerization initiator represented by the general formula (1) used in the present invention, R ¹ represents a linear or branched carbon atom number of 1 to 10 An alkyl group or a vinyl group, Y represents a hydrogen atom, a linear or branched alkyl group with 1 to 10 carbon atoms (-R ² may be omitted, but R ² represents an alkyl group) 6 to 10 carbon atoms The aryl group (may be omitted as -Ar ¹ , but Ar ¹ represents an aryl group), linear or branched alkoxy with 1 to 10 carbon atoms (may be omitted as -OR ³ , but R ³ represents an alkyl group), or an aryloxy group with 6 to 10 carbon atoms (-OAr ² may be omitted, but Ar ² represents an aryl group). Here, R ² and R ³ represent the same groups as R ¹ .

(1)

(1)

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ¹ to R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, di Butyl, tertiary butyl, pentyl, amyl, isopentyl, hexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, Isononyl, decyl, etc.

Examples of the aryl group having 6 to 10 carbon atoms represented by Ar ¹ or Ar ² include phenyl, naphthyl, azulenyl, indenyl, indenyl, and tetrahydronaphthyl.

啉基丙-1-酮等。In the aforementioned general formula (1), R ¹ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group having 1 carbon atom. Furthermore, Y is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and a hydrogen atom is particularly preferred. Examples of the aforementioned photopolymerization initiator related to the present invention include 1-([1,1'-biphenyl]-4-yl)-2-methyl-2-

Linyl-1-propanone and so on.

In the present invention, the content of the photopolymerization initiator represented by the aforementioned general formula (1) is preferably 0.5-20% by mass, more preferably 1.0-15% by mass relative to the total solid content of the ink. In the case of 0.5% by mass or less, the active free radicals generated by ultraviolet radiation will be inactivated by oxygen in the air, and the curability of the ink will be significantly reduced. Therefore, the odor of unreacted materials from the ink raw material becomes strong, or the surface of the printed matter is scratched, causing poor appearance, or when the surface of the printed matter overlaps and accumulates on the back of the printed matter discharged onto the printed matter. A defect called adhesion occurs when the surface of the printed matter is in close contact with the back of the printed matter above it. On the other hand, in the case of 20% by mass or more, the possibility of the photopolymerization initiator being precipitated becomes very high, and the initiator may be precipitated in the ink within a few days after the production of the ink, making it impossible to express Ink hardening performance as designed. Furthermore, there is a possibility that the particles of the initiator precipitated in the printing ink may accumulate on the cylinder or plate of the printing press, making it impossible to form a correct image.

啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮等的化合物。[Combined use of universal photopolymerization initiator] In the present invention, in addition to the photopolymerization initiator represented by the aforementioned general formula (1), in view of the type of ultraviolet light source used, in the range that does not impair the effects of the present invention, The irradiation intensity of the ultraviolet light source, the cumulative light quantity of ultraviolet irradiation, the color, the printing film thickness, the hygiene, etc., may also be suitably used in combination with a general-purpose photopolymerization initiator. If one example is given, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl -1-Phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy -1-{4-[4-(2-hydroxy-2-methyl-propanyl)-benzyl]phenyl}-2-methyl-propan-1-one, methyl phenylglyoxylate, Hydroxyphenylacetic acid, a mixture of 2-[2-side oxy-2-phenylacetoxyethoxy]ethyl ester and hydroxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl ester, 1 ,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzyloxime)], ethyl ketone, 1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl)-,1-(O-acetyloxime), 2-methyl-1-(4-methylthiophenyl)-2-

Linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Alkylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

(Alkolinyl)phenyl]-1-butanone and other compounds.

Also, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2, ,6-Dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide and other phosphine oxide compounds.

In addition, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-bis Isopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-Dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxy Thioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-pendant -9H thioxanthone-2-yloxy-N,N,N-trimethyl-1-propylamine Thioxanthone compounds such as hydrochloride.

In addition, 4,4'-diones such as 4,4'-bis-(dimethylamino)diphenyl ketone and 4,4'-bis-(diethylamino)diphenyl ketone can be cited Diphenyl ketone compounds such as phenylamino benzophenones and 4-benzyl-4'-methyldiphenyl sulfide.

In addition, for example, diphenyl ketone, 4-methyl-diphenyl ketone, 2,4,6-trimethyl diphenyl ketone, 2,3,4-trimethyl diphenyl ketone, 4 -Phenyl diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone, 4-(1,3-propenyl-1,4,7,10,13-pentaside Oxytridecyl) benzophenone, methyl benzoyl benzoate, [4-(methylphenylthio) phenyl] phenyl ketone, diethoxy acetophenone, Dibutoxy acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, etc.

In the present invention, the aforementioned general-purpose photopolymerization initiator used in combination with the photopolymerization initiator represented by the aforementioned general formula (1) may be used alone or in combination of several kinds. Among them, it is preferable to use the photopolymerization initiator represented by the aforementioned general formula (1) and the phosphine oxide compound in combination, and in particular, from the viewpoint of solubility to the resin, the combination of 2,4,6-tri Methylbenzyl diphenylphosphine oxide is more preferable. In the case of combined use, the content of 2,4,6-trimethylbenzyldiphenylphosphine oxide is 70 to 2000% by mass relative to the photopolymerization initiator represented by the aforementioned general formula (1) It is better to contain in the form of, more preferably 70-1000% by mass. Moreover, in the case of combined use, the amount of 2,4,6-trimethylbenzyldiphenylphosphine oxide used is preferably 1.0-15% by mass relative to the total solid content of the ink, 3.0 ~10% by mass is more preferable. If it is less than 1.0% by mass, a sufficient effect of improving the curability cannot be obtained. If it exceeds 15% by mass, unreacted phosphine oxide will still remain in the cured coating film after UV irradiation. The hue changes to an unacceptable degree of yellow, or the initiator precipitates, or the fluidity of the ink is significantly reduced.

[Sensitizers and light starter additives] In the present invention, in addition to the photopolymerization initiator represented by the general formula (1) or the aforementioned general-purpose photopolymerization initiator, it is preferable to use a photosensitizer or a photoinitiator auxiliary such as a tertiary amine in combination. . The photosensitizer is not particularly limited. Examples include thioxanthone, 4,4'-bis(diethylamino)benzophenone and other diphenylketones, anthraquinones, Coumarin series and so on. Among these, especially 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone Thioxanthone compounds such as ketone, 2-chlorothioxanthone, 2-isopropylthioxanthone, or Michelone, 4,4'-bis-(diethylamino)benzophenone, etc. 4,4'-Dialkylamino benzophenones are preferred. From the standpoints of performance, safety, or ease of acquisition, 2,4-diethylthioxanthone, 2-isopropyl Thioxanthone and 4,4'-bis-(diethylamino)diphenyl ketone are particularly preferred. When a sensitizer or a photo-initiating auxiliary is used in combination, it is preferably 0.05-10% by mass, and more preferably within a range of 0.1-7.0% by mass relative to the total solid content of the ink. When it is less than 0.05% by mass, sufficient curability improvement effect cannot be obtained. When it exceeds 10% by mass, the hue of the cured coating film may change to an unacceptable degree of yellow, or the sensitizer may precipitate, or the ink may be printed. The liquidity is significantly reduced.

On the other hand, tertiary amines are not particularly limited, but examples include p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, N,N-dimethyl Benzylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-dihydroxyethylaniline, triethylamine and N,N -Dimethylhexylamine, etc., which can reduce the polymerization hindrance caused by oxygen, or react with thioxanthones and 4,4'-dialkylamino benzophenones activated by ultraviolet rays to become active free radicals The donor body improves the hardening performance of the ink. The tertiary amine is preferably used in combination within a range that does not impair the printing performance of the active energy ray-curable ink of the present invention. Relative to the total solid content of the ink, it is preferably 0.1-10% by mass, between 0.1- It is better to use the range of 5.0% by mass.

In addition, in applications requiring high hygiene, a high-molecular-weight compound in which multiple photosensitizers or tertiary amines are branched with polyhydric alcohols in one molecule can also be suitably used.

(Monomers with ethylenically unsaturated double bonds) The active energy ray-curable monomer and or oligomer used in the present invention can be used without particular limitation as long as it is a monomer and or oligomer used in the active energy ray-curable technical field. In particular, those having a (meth)acryloyl group, vinyl ether group, etc. as the reactive group are preferred. Also, the number of reaction groups or molecular weight is not particularly limited. The more the number of reaction groups, the higher the reactivity, but the viscosity or crystallinity tends to increase. In addition, the higher the molecular weight, the higher the viscosity, so it can respond The desired physical properties are appropriately combined and used. For example, at the point where it is properly cured by low-energy irradiation like UV-LED, in order to combine a more reactive trifunctional or higher active energy ray curable monomer, the adhesiveness on the printing substrate can be obtained due to the application. The necessary physical properties such as the flexibility of the film are preferably used alone or in combination with monofunctional and difunctional monomers.

Specifically, for example, monofunctional (meth)acrylates, polyfunctional (meth)acrylates, polymerizable oligomers, etc., which have a proven track record in the lamp method, can also be directly used in the ultraviolet light emitting diode described in the present invention. In the style.

Examples of monofunctional (meth)acrylates include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, ( Lauryl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, (meth) Isodecyl acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxy (meth)acrylate Ethyl ethyl, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, methyl tetrahydrofuran (meth)acrylate , Glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxy (meth)acrylate Propyl ester, diethylaminoethyl (meth)acrylate, nonylphenoxyethyl tetrahydrofuran methyl (meth)acrylate, caprolactone modified tetrahydrofuran methyl (meth)acrylate, (methyl) Isobornyl acrylate, dicyclopentyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, etc.

Examples of (meth)acrylates having two or more functions include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butane 2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate and other diol di(meth)acrylic acid Ester, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ginseng (2-hydroxyethyl) trimeric isocyanate di(meth)acrylate, new to 1 mol Diol bis(meth)acrylate obtained by adding more than 4 moles of ethylene oxide or propylene oxide to pentanediol, and adding 2 moles of ethylene oxide to 1 mole of bisphenol A Or diol di(meth)acrylate obtained from propylene oxide, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, neopentaerythritol tri(meth)acrylic acid Polyols such as poly(meth)acrylate ester, neopentylerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, poly(meth)acrylate of dineopentaerythritol, etc. Poly(meth)acrylate, triol tri(meth)acrylate obtained by adding more than 3 moles of ethylene oxide or propylene oxide to 1 mol of glycerol, and 1 mol of triol Triol bis or tri(meth)acrylate obtained by adding 3 moles or more of ethylene oxide or propylene oxide to methylol propane, and adding 4 moles or more to 1 mole of bisphenol A Poly(meth)acrylate of polyoxyalkylene polyol such as di(meth)acrylate of diol obtained from ethylene oxide or propylene oxide.

Examples of polymerizable oligomers include amine-modified polyether acrylate, amine-modified epoxy acrylate, amine-modified aliphatic acrylate, amine-modified polyester acrylate, amino (meth)acrylate, etc. Amine modified acrylate, thiol modified polyester acrylate, thiol (meth)acrylate and other thiol modified acrylate, polyester (meth)acrylate, polyether (meth)acrylate , Polyolefin (meth)acrylate, polystyrene (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, etc.

In addition, as the aforementioned active energy ray-curable monomers and or oligomers, tetrafunctional or higher (meth)acrylates are used in paper such as fine paper, coated paper, art paper, molded paper, tissue paper, and thick paper. In printing applications, since it is of great help to the improvement of hardening or strength, it is preferably used. Relative to the total solid content of the ink, it is better to use it in the range of 15-70% by mass. On the other hand, for printing on plastics, as the crosslinking density of the cured coating film increases, the adhesion between the substrate and the cured coating film will decrease. Therefore, it is necessary to appropriately reduce the tetrafunctional or higher (meth)acrylic acid. The content of esters. In this case, the (meth)acrylate having four or more functions is preferably used in a range of 0-50% by mass relative to the total solid content of the ink.

The active energy ray-curable printing ink of the present invention uses the monomer having ethylenically unsaturated double bonds and the photopolymerization initiator represented by the general formula (1) as essential components. In addition, resins or pigments can also be used , Various additives.

(Resin) As the resin, various known and commonly used binder resins can be used. The binder resin described here refers to the entire resin that has appropriate pigment affinity and dispersibility, and has rheological properties required for printing inks. For example, non-reactive resins include diallyl phthalate Ester resin, epoxy resin, epoxy ester resin, polyurethane resin, polyester resin, petroleum resin, pine ester resin, poly(meth)acrylate, cellulose derivative, vinyl chloride-vinyl acetate Copolymers, polyamide resins, polyvinyl acetal resins, butadiene-acrylonitrile copolymers, etc., and epoxy acrylate compounds having at least one polymerizable group in the molecule, and urethane Ester acrylate compounds, polyester acrylate compounds, etc., these binder resins may be used alone or in combination of any one or more of them.

Among them, if the photopolymerization initiator represented by the aforementioned general formula (1) is used in combination with diallyl phthalate resin, in addition to improving the curability of the active energy ray-curable ink, the ink can also be improved Its fluidity can prevent the occurrence of defects in printability, such as container cracks on the printing press and poor transfer between ink rollers.

顏料、硫靛顏料、蒽醌系顏料、喹啉黃顏料、金屬錯合物顏料、二酮吡咯并吡咯顏料、碳黑顏料、其他多環式顏料等。(Pigment) as pigments include known commonly colored with organic pigments include, for example, "organic pigment Manual (Author: Isao Hashimoto, Publisher: COLOR OFFICE, early 2006 edition)" the mortgage contains a printing ink with organic pigments Etc., soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindoline Ketone pigments, isoindoline pigments, two

Pigments, thioindigo pigments, anthraquinone pigments, quinoline yellow pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, other polycyclic pigments, etc.

In addition, in the active energy ray curable ink of the present invention, inorganic fine particles can also be used as an extender pigment. Examples of inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, and zinc white; calcium carbonate powder, precipitating calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous earth, talc, kaolin, and alumina Inorganic pigments such as inorganic pigments such as aluminum white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, polishing powder, etc., or silicone, glass beads, etc. These inorganic fine particles can be used in the printing ink in the range of 0.1 to 60% by weight to adjust the coloring or rheological properties of the printing ink.

(Other additives) In terms of other additives, for example, as additives that impart friction resistance, anti-blocking properties, sliding properties, and scratch resistance, examples include carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, etc. Natural waxes, Fischer-Tropsch waxes, polyethylene waxes, polypropylene waxes, polytetrafluoroethylene waxes, polyamide waxes, and synthetic waxes such as polysiloxanes.

、對苯醌、亞硝基苯、2,5-二-三級丁基-對苯醌、二硫基苯甲醯基二硫醚、苦味酸、銅鐵靈、鋁N-亞硝基苯基羥基胺、三-對硝基苯基甲基、N-(3-氧基苯胺基-1,3-二甲基亞丁基)苯胺氧化物、二丁基甲酚、環己酮肟甲酚、癒創木酚、鄰異丙基酚、丁醛肟、甲基乙基酮肟、環己酮肟等的聚合抑制劑。In addition, for example, as additives that impart storage stability to printing inks, (alkyl)phenols, hydroquinones, catechol, resorcinol, p-methoxyphenol, tertiary butyl catechol, tertiary butyl can be exemplified Hydroquinone, gallic phenol, 1,1-trinitrophenylhydrazine, phenanthrene

, P-benzoquinone, nitrosobenzene, 2,5-di-tertiary butyl-p-benzoquinone, dithiobenzyl disulfide, picric acid, copper iron spirit, aluminum N-nitrosobenzene Hydroxyamine, tris-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylene) aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, It is a polymerization inhibitor for wood phenol, o-isopropylphenol, butyrald oxime, methyl ethyl ketoxime, cyclohexanone oxime, etc.

In addition, additives such as ultraviolet absorbers, infrared absorbers, and antibacterial agents can be added according to the required performance.

The active energy ray-curable printing ink of the present invention can be used without a solvent, and an appropriate solvent can also be used as necessary. The solvent is not particularly limited as long as it does not react with the above-mentioned components, and it can be used alone or in combination of two or more.

The active energy ray-curable printing ink of the present invention can be carried out by the same method as in the past. For example, the aforementioned pigment, resin, acrylic monomer or oligomer, and polymerization inhibitor are added at room temperature to 100°C. , Ink composition components such as sensitizers such as initiators, amine compounds, and other additives, using kneaders, three-roll mills, attritors, sand mills, frame mixers, etc. Adjust the machine to manufacture.

(Method of manufacturing hardened ink, printed matter) The ink cured product of the present invention is characterized in that the active energy ray hardening type ink is used for printing on a substrate, and the active energy ray is used to harden the printed ink.

(Printing method) The active energy ray-curable printing ink of the present invention, as described above, can be particularly suitable for printing inks that will be attached to flat plates for lithographic printing (lithographic printing using dampening water or non-level plate printing without dampening water). After being transferred to an intermediate transfer body such as a blanket, the lithographic offset printing method combined by the transfer (offset printing) method of printing to the printed body is used (the following will be the active energy printed by the lithographic offset printing method Line hardening ink is called active energy ray hardening ink for offset printing).

Hereinafter, a specific aspect of the case of using the active energy ray curable ink of the present invention as an active energy ray curable ink for lithographic offset printing will be described.

The active energy ray-curable ink for offset printing is a high-viscosity ink of 5-100Pa･s. The mechanism of the lithographic printing machine is: the printing ink is supplied to the image part of the plate through the ink pot of the printing press through a plurality of cylinders. In the lithographic printing using dampening water, the dampening water is supplied to the non-image Part, the ink is discharged, and an image is formed on the paper.

In the lithographic printing process using dampening water, the emulsification balance between the printing ink and the dampening water is important, and the printing ink also requires high-speed printability with emulsification resistance. If the emulsification amount of the printing ink is too high, the printing ink will also become easy to be printed on the non-image area and cause pollution, or the printing density will be reduced, the emulsified printing ink will be entangled on the water roller, the ink will fly, and the printing ink will accumulate on the feed. Bad printing of blankets on the outside of the paper. If the amount of emulsification is small, during printing with few patterns, contamination of the non-image area called a dirty plate becomes significant, making it difficult to print stably. From this point of view, in the active energy ray-curable ink for lithographic offset printing of the present invention, the acid value of the resin or monomer used in the ink is preferably in the range of 1.0 to 10.0, preferably in the range of 1.0 to 2.0. The range is better. If the acid value of the ink is higher than 10.0, the ink becomes easy to emulsify. If the supply of dampening water during printing increases, the density of the printed matter decreases, or the emulsified ink easily adheres to the non-hydrophilized plate. The image part, therefore, the non-image part of the printed matter will cause contamination called dirty. On the other hand, if the acid value of the ink is less than 1.0, the fluidity of the ink or the gloss of the printed matter will decrease.

(Printing substrate) The substrate used is not particularly limited, as long as the paper or plastic substrate generally used in the field of offset printing and the flexible packaging substrate used in the field of food packaging can be used. For example, if it is paper, it can be high-quality paper, kraft paper, plain white roll used for printing catalogs, posters, advertising leaflets, CD cases, direct mail, brochures, packaging for cosmetics or beverages, pharmaceuticals, toys, machines, etc. Paper such as tube paper, cellophane, parchment, Manila cardboard, white corrugated paper, coated paper, art paper, molded paper, thin paper, thick paper, etc., various synthetic papers, etc.

In addition, as a plastic substrate or a flexible packaging substrate, for example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA) can be cited; OPP (Biaxially stretched polypropylene) films such as polyolefin resin films; polystyrene resin films; polyamide resin films such as nylon 6, parylene hexadiamide (MXD6 nylon), etc.; polycarbonate resins Film; polyacrylonitrile resin film; polyimide resin film; these laminates (such as nylon 6/MXD6/nylon 6, nylon 6/ethylene-vinyl alcohol copolymer/nylon 6) or mixed Polyethylene such as low-density polyethylene (LDPE) or linear low-density polyethylene (LLDPE) or high-density polyethylene (HDPE) used especially as a sealing film, acid-modified polyethylene, polypropylene ( PP), acid-modified polypropylene, copolymerized polypropylene, VMCPP (aluminum vapor deposited non-extended polypropylene), VMLDPE (aluminum vapor deposited low density polyethylene), ethylene-vinyl acetate copolymer, ethylene-(methyl) Resin films such as polyolefin resins such as acrylate copolymers, ethylene-(meth)acrylic acid copolymers, and ionomers. In addition, there are also soft metal foils provided with aluminum foil and the like for imparting various functions such as masking functions to the aforementioned resin film; aluminum vapor deposition, silicon dioxide vapor deposition, alumina vapor deposition, and silica alumina binary Evaporation layer such as vapor deposition; composite film containing vinylidene chloride resin, modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon and other organic shielding layers.

Among the aforementioned substrates, resin films used for plastic substrates or flexible packaging substrates generally have low surface energy and poor wettability to UV-curable offset printing inks, and therefore tend to cause poor adhesion. Therefore, a corona discharge is generated by applying a high-frequency and high-voltage output supplied from a high-frequency power supply between the discharge electrode and the ground roller of the corona treatment device, and the aforementioned film is passed through by the corona discharge. It is better to increase the surface energy of the aforementioned substrate.

In addition, generally speaking, it is preferable to apply an adhesion imparting agent called a primer or an anchor (coating agent) to the aforementioned plastic substrate or flexible packaging substrate in advance.

By lithographic offset printing, the active energy ray hardening ink is transferred and printed on these substrates to set the ink layer. Generally speaking, the printing using offset printing method is a method of overlapping printing with single color or multi-color using four-color ink or special ink. Flat offset printing presses have been manufactured and sold by many printing press manufacturers. As an example, Heidelberg, Komori Corporation, RYOBI MHI Graphic Technology, Manroland, KBA, etc., and a single sheet of printing paper are used. The present invention can be suitably used in an offset printing press and an offset web printing press using a roll-shaped printing paper in any paper supply method. More specifically, offset printing presses such as the Speedmaster series manufactured by Heidelberg, the Lithrone series manufactured by Komori Corporation, and the RMGT series manufactured by RYOBI MHI Graphic Technology are mentioned.

(Light source) As the active energy source used for the purpose of curing the ink for printing, for example, germicidal lamps, fluorescent lamps for ultraviolet light, ultraviolet light emitting diodes (UV-LED), carbon arc, xenon lamp, High-pressure mercury lamps for copying, medium or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light and other ultraviolet light as the light source. In terms of the ultraviolet light-emitting diode (UV-LED), and its peak wavelength at about 350 ~ 420nm is preferred, more preferably in the range of 350 ~ 400nm, the cumulative amount of light 5mJ / cm ² ~ 200mJ / cm ² or so More desirably, 10-100 mJ/cm ² is preferred.

In addition, with regard to the irradiation intensity (mW/cm ² ) of the ultraviolet light emitting diode, the appropriate irradiation intensity range depends on the number of ultraviolet light emitting diode light sources arranged along the printing direction, the irradiation distance from the light source to the composition, etc. The conditions vary, so there is no special regulation, but the moving speed of the printing substrate in the printing method described in the present invention is about 60-400m/min. Therefore, for the UV curing on the printing substrate moving at this printing speed For the sexual composition, it is preferable to use the irradiation intensity at which the integrated light intensity value becomes the aforementioned level.

The active energy ray-curable printing ink of the present invention is generally suitable for lithographic offset printing using wetting water, but is also suitable for waterless printing without using wetting water. In addition, the active energy ray-curable printing ink of the present invention can be applied to various packaging printing materials such as foam printing materials, various book printing materials, carton paper, etc., various plastic printing materials, sticker/label printing materials, art printing materials, and metal Printed materials (art prints, beverage can prints, food prints such as cans), etc. Furthermore, it is sometimes used as an overcoat varnish. [Example]

Hereinafter, the examples are further explained in detail, but the present invention is not limited by these.

[Manufacturing method of active energy ray hardening ink] According to the composition of Table 1 and Table 2, the active energy ray curable inks of Examples 1 to 7 and Comparative Examples 1 to 7 were kneaded with a three-roll mill to obtain various active energy ray curable inks. In addition, an empty column in the table means no blending.

[Manufacturing method of color exhibit] The active energy ray hardening type ink obtained in this way is used in a simple color developing machine (RI TESTER, manufactured by Toyoei Seiko Co., Ltd.), and 0.10 ml of ink is used. Spread evenly on the rubber roller and the metal roller. On the PET raw film (made by DIC Corporation, DAITAC UVPET transparent 25FL), the printing density is 1.8 (based on the SpectroEye density of X-Rite) in the entire area of about 220cm ² To measure) evenly coat and spread the color to make the color development. In addition, the so-called RI TESTER is a testing machine that spreads ink on paper or film, and can adjust the amount of ink transfer or printing pressure.

(Drying method using ultraviolet light emitting diode light source) Using a water-cooled UV-LED (central emission wavelength 385nm±5nm UV-LED output 100%) and a UV irradiation device (manufactured by EyeGraphics) with a belt conveyor, the color development object is placed on the conveyor at 100m/min The conveyor speed makes it pass directly below the LED (irradiation distance 9cm). Ultraviolet (UV) irradiation is performed on the color vehicle after application of the photocurable ink obtained by the aforementioned method to harden and dry the ink film.

[Method for evaluating curability of active energy ray curable ink] Immediately after hardening, the hardened ink layer was scratched with a nail to evaluate the hardening of the hardened film. The evaluation criteria are as follows. ◎: Even if it is scratched with strong force, it will not scratch, and the UV curability is very good. ○: If scratched with strong force, it will scratch slightly. △: If scratched with strong force, scratches are obvious. ×: Even if it is scratched with a weak force, the scratches are obvious, and the UV curability is poor.

[Method of evaluating odor of hardened coating film] The hardened product hardened by the aforementioned hardening method was cut into a length of 5 cm and a width of 2.5 cm to prepare 10 slices. Quickly put 10 pieces of this slice into a collection bottle with an outer diameter of 40mm, a height of 75mm, an inner diameter of 20.1mm, and a capacity of 50ml. The cap was fastened and stored in a thermostat at 60°C for 1 hour to fill the collection bottle with odor. gas. Next, the collection bottle was placed at room temperature, and the odor intensity of each sample was evaluated in 10 stages by 10 monitors who evaluated the odor intensity. The odor evaluation results of 10 persons were averaged and determined as the odor intensity of the sample. In addition, the higher the value, the weaker the odor. ○: 10～7 △: 6～3 ×: 2～0

[Evaluation method of active energy ray hardening ink 3: Flowability] The ink fluidity is measured by the method specified in JIS K5101,5701 by the parallel plate viscometer method (Spread Meter). The ink sandwiched between two parallel plates placed horizontally is observed from time to time because of the load plate. The characteristic of spreading into concentric circles under its own weight (115 grams). The spreading diameter of the ink after 60 seconds is set as the diameter value (DM[mm]), and the following three stages are used to evaluate the ink printability. . In this evaluation item, when the DM has a composition smaller than 27 mm, defects in printability such as container cracks on the printing press and poor transfer between ink rollers are likely to occur. ○: DM30mm or more △: Above DM27mm～less than 30mm ×: DM is less than 27mm

[Lift offset printing method of active energy ray hardening ink] Regarding the active energy ray-curable printing inks of the manufactured Examples 1-7 and Comparative Examples 1-7, the offset printing suitability was evaluated. As the ultraviolet irradiation device, a Manroland offset printing machine (ROLAND R700 printing machine, 40-inch wide machine) equipped with a water-cooled metal halide lamp manufactured by EyeGraphics (output 160W/cm, using three lamps) was used. Implementation of offset printing at the printing speed. The printing paper used OK top coat-Plus (57.5kg, A version) manufactured by Oji Paper Co., Ltd. The wetting water supplied to the plate surface was an aqueous solution obtained by mixing 98% by weight of tap water and 2% by weight of H liquid (FST-700, manufactured by DIC Graphics).

[Evaluation method of active energy ray curable ink composition 3: Offset printing suitability] As a method for evaluating the printability of offset ink, first set the water supply scale of the printer to 40 (standard water volume), and operate the ink supply key to make the printed matter density become standard program blue density 1.6 (spectroEye manufactured by X-Rite) Densitometer for measurement), fix the ink supply key at the time when the density is stable. Then, under the condition that the ink supply key is fixed, the water supply scale is changed from 40 to 55, and 300 sheets are printed under the condition of increasing the water supply amount, and the blue density of the printed matter after 300 sheets is measured. In the state of increasing the water supply, the less the density of the printed matter decreases, the more it can be rated as an ink with excellent emulsification and printability. The printability of the active energy ray-curable ink was evaluated according to the following criteria. ○: The blue density of the printed matter is 1.5 or more, and the offset printing suitability is good. △: The blue density of the printed matter is 1.4 or more to less than 1.5, and the offset printing suitability is moderate. ×: The blue density of the printed matter is less than 1.4, and the offset printing suitability is poor.

The results are disclosed in the table.

[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Raw material name RAVEN 1060Ultra 16 16 16 16 16 16 16 Fastogen Blue TGR-1 3 3 3 3 3 3 3 Hostaperm RL 02 2 2 2 2 2 2 2 High filler 5000PJ 2 2 2 2 2 2 2 S-381-N1 2 2 2 2 2 2 2 Diallyl phthalate resin varnish 29 29 29 29 Miramer PE-210 29 29 29 ARONIX M-400 28 28 28 28 28 28 28 SR355NS 7 7 7 7 7 7 4.7 STEARER TBH 1 1 1 1 1 1 1 Photopolymerization initiator B 2 2 2 2 5 5 12 Omnirad 907 Omnirad TPO 6.7 6.7 6.7 6.7 Omnirad DETX 0.3 0.3 Omnirad EMK 0.3 0.3 4 4 0.3 Omnirad EDB 1 1 1 1 1 1 total 100 100 100 100 100 100 100 385nm LED hardening ○ ◎ ○ ◎ ○ ◎ ◎ Stench ○ ○ ○ ○ ○ ○ ○ fluidity △ ○ △ ○ △ ○ ○ Offset printing suitability ○ ○ ○ ○ ○ ○ ○

[Table 2] Table 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Raw material name RAVEN 1060Ultra 16 16 16 16 16 16 16 Fastogen Blue TGR-1 3 3 3 3 3 3 3 Hostaperm RL 02 2 2 2 2 2 2 2 High filler 5000PJ 2 2 2 2 2 2 2 S-381-N1 2 2 2 2 2 2 2 Diallyl phthalate resin varnish 29 29 29 29 Miramer PE-210 29 29 29 ARONIX M-400 28 28 28 28 28 28 28 SR355NS 7 7 7 7 7 7 4.7 STEARER TBH 1 1 1 1 1 1 1 Photopolymerization initiator B Omnirad 907 2 2 2 2 5 5 12 Omnirad TPO 6.7 6.7 6.7 6.7 Omnirad DETX 0.3 0.3 Omnirad EMK 0.3 0.3 4 4 0.3 Omnirad EDB 1 1 1 1 1 1 total 100 100 100 100 100 100 100 385nm LED hardening △ ○ △ ○ ○ ○ ○ Stench × × × × × × × fluidity × △ △ ○ △ ○ △ Offset printing suitability ○ ○ ○ ○ ○ ○ ○

啉基丙-1-酮The details of the raw materials used are as follows. "RAVEN 1060Ultra": Carbon black made by BIRLA CARBON "FASTOGEN BLUE TGR-1": Pigment Blue made by DIC 15:3 "Hostaperm Violet RL 02": Pigment Violet 23 made by Clariant "High filler #5000P": Talc made by Matsumura Sangyo "S -381-N1": Shamrock-made olefin-based fine powder wax "Miramer PE-210": Miwon-made bisphenol A epoxy acrylate oligomer "diallyl phthalate resin varnish": Osaka SODA-made DAISO DAP A mixture of 35 mass% dissolved in SR355NS 65% by mass "STEARER TBH": Tertiary butyl hydroquinone manufactured by Seiko Chemicals "ARONIX M-400": Dineopentaerythritol pentaerythritol penta and hexaacrylate "SR355NS" manufactured by Toagosei : Di-trimethylolpropane tetraacrylate manufactured by Arkema "Photopolymerization initiator B": Among the photopolymerization initiators described in (1), the compound 1-([1, 1'-Biphenyl]-4-yl)-2-methyl-2-

Linylpropan-1-one

(3)

(3)

啉基丙-1-酮 Omnirad TPO 2,4,6-三甲基苯甲醯基-二苯基膦氧化物 Omnirad DETX 2,4-二乙基噻噸酮 Omnirad EMK 4,4’-雙(二乙基胺基)二苯基酮 Omnirad EDB 4-(二甲基胺基)安息香酸乙酯The following photopolymerization initiators are all manufactured by IGM RESINS. Omnirad 907 2-methyl-1-[4-(methylthio)phenyl]-2-

Omnirad TPO 2,4,6-trimethylbenzyl-diphenylphosphine oxide Omnirad DETX 2,4-Diethylthioxanthone Omnirad EMK 4,4'-bis( Diethylamino) diphenyl ketone Omnirad EDB 4-(dimethylamino) ethyl benzoate

From this result, it is clear that the active energy ray-curable ink system of Examples 1 to 7 is excellent in curability.

no.

no.

Claims (8)

An active energy ray-curable printing ink characterized by containing: a monomer having an ethylenically unsaturated double bond and a photopolymerization initiator represented by the general formula (1),

(1) (In the general formula (1), R ¹ represents a linear or branched alkyl group having 1 to 10 carbon atoms, or a vinyl group, and Y represents a hydrogen atom, a linear or branched chain having 1 to 10 carbon atoms An alkyl group, an aryl group having 6 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms). The active energy ray-curable ink of claim 1, wherein the photopolymerization initiator represented by the aforementioned general formula (1) is 1-([1,1'-biphenyl]-4-yl)-2- Methyl-2-

Alkylpropan-1-one. Such as the active energy ray-curable ink of claim 1 or 2, which contains an phosphine oxide-based photopolymerization initiator and/or a photosensitizer. The active energy ray-curable ink of any one of claims 1 to 3 contains a tertiary amine compound. For example, the active energy ray-curable printing ink of any one of claims 1 to 4 is suitable for offset printing. A method for manufacturing a hardened printing ink, which is characterized by using the active energy ray hardening type ink according to any one of claims 1 to 5 for printing, and using the active energy ray to harden the printed ink. A method for manufacturing a hardened printing ink, which is characterized by using the active energy ray hardening type ink as claimed in any one of claims 1 to 5 for offset printing, and using the active energy ray to harden the printed ink . A printed matter obtained by a method for manufacturing a hardened ink such as Claim 6 or 7.